Resolution of protected silaproline for a gram scale preparation

Martin, Charlotte; Vanthuyne, Nicolas; Miramon, Hélène; Martinez, Jean; Cavelier, Florine

doi:10.1007/s00726-011-1112-y

Cited by 15 publications

(9 citation statements)

References 17 publications

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“…This amino acid was introduced independently by 2 groups about 2 decades ago . However, despite the growing interest in this amino acid, studies are hampered by their somewhat limited availability …”

Section: Introductionmentioning

confidence: 99%

Exploring hydrophobicity limits of polyproline helix with oligomeric octahydroindole‐2‐carboxylic acid

Kubyshkin

Budiša

2018

Journal of Peptide Science

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The polyproline-II helix is the most extended naturally occurring helical structure and is widely present in polar, exposed stretches and "unstructured" denatured regions of polypeptides. Can it be hydrophobic? In this study, we address this question using oligomeric peptides formed by a hydrophobic proline analogue, (2S,3aS,7aS)-octahydroindole-2-carboxylic acid (Oic). Previously, we found the molecular principles underlying the structural stability of the polyproline-II conformation in these oligomers, whereas the hydrophobicity of the peptide constructs remains to be examined. Therefore, we investigated the octan-1-ol/water partitioning and inclusion in detergent micelles of the oligo-Oic peptides. The results showed that the hydrophobicity is remarkably enhanced in longer oligomeric sequences, and the oligo-Oic peptides with 3 to 4 residues and higher are specific towards hydrophobic environments. This contrasts significantly to the parent oligoproline peptides, which were moderately hydrophilic. With these findings, we have demonstrated that the polyproline-II structure is compatible with nonpolar media, whereas additional manipulations of the terminal functionalities feature solubility in extremely nonpolar solvents such as hexane.

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Section: Introductionmentioning

confidence: 99%

Exploring hydrophobicity limits of polyproline helix with oligomeric octahydroindole‐2‐carboxylic acid

Kubyshkin

Budiša

2018

Journal of Peptide Science

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“…The deprotected ( d )Sip starting material was obtained from acid treatment of enantiopure Boc‐( d )Sip‐O t ‐Bu . The N ‐carbamoyl intermediate synthesis was very easily monitored since the reaction mixture became totally transparent when all the starting amino acid was reacted.…”

Section: Resultsmentioning

confidence: 99%

“…The deprotected (D)Sip starting material was obtained from acid treatment of enantiopure Boc-(D)Sip-Ot-Bu. 11 The N-carbamoyl intermediate synthesis was very easily monitored since the reaction mixture became totally transparent when all the starting amino acid was reacted. In the case of Sip, we observed the presence of NCA in higher proportion (50%) than for proline (33%), the spontaneous cyclization being facilitated by the less constrained five-membered ring 7,8,25 (Scheme 3, Fig.…”

Section: Monomer Synthesismentioning

confidence: 99%

“…Sip was synthesized successfully via asymmetric synthesis by Schollköpf method, but with this approach the scale up was difficult. More recently, a racemic synthesis was carried out for the gram scale preparation of enantiomerically pure Sip, requiring resolution of the enantiomers by chiral high performance liquid chromatography (HPLC) …”

Section: Introductionmentioning

confidence: 99%

“…More recently, a racemic synthesis was carried out for the gram scale preparation of enantiomerically pure Sip, requiring resolution of the enantiomers by chiral high performance liquid chromatography (HPLC). 11 In this context, we thought that it could be interesting to demonstrate the possibility to synthesize both polyproline and polysilaproline by polymerization of corresponding amino acid NCA.…”

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confidence: 99%

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Synthesis of homopolypeptides with PPII structure

Martin

Lebrun

Martinez

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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Polyprolines are attractive polymers because of their folding property into polyproline II (PPII) structure, their significance in protein/protein interactions, and their potential as new therapeutic targets. Silaproline (Sip) is an analogue of proline, which exhibits similar conformational properties. The presence of dimethylsilyl group confers to Sip a higher lipophilicity as well as an improved resistance to biodegradation. Enantiomerically pure Sip was available in gram quantities from resolution of the enantiomers by chiral high performance liquid chromatography. This study describes the first synthesis of Sip N-carboxyanhydride (NCA) and shows preliminary results on comparison of polymerization of (L)Pro-NCA and (D)Sip-NCA to obtain homopolypeptides with PPII structure, polyproline, and polysilaproline polymers. V C 2013

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α‐Sila‐Dipeptides: Synthesis and Characterization

et al. 2018

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The first two a-sila-dipeptides, 7 and cyclo-siladipeptide 8,w ere synthesized and characterized by several methods,i ncluding X-rayc rystallography.B ulkyt -BuMe 2 Si substituents provides ome kinetic stabilization to the synthesized molecules. 7 and 8 are the first examples of a" Si for C switch"inthe central a-position of an amino acid or apeptide, in whichsilicon is bonded to both the amino and the carbonyl groups.

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Resolution of protected silaproline for a gram scale preparation

Cited by 15 publications

References 17 publications

Exploring hydrophobicity limits of polyproline helix with oligomeric octahydroindole‐2‐carboxylic acid

Exploring hydrophobicity limits of polyproline helix with oligomeric octahydroindole‐2‐carboxylic acid

Synthesis of homopolypeptides with PPII structure

α‐Sila‐Dipeptides: Synthesis and Characterization

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